Rovibrational computation of H$_3^+$ with permutationally invariant Pekeris coordinates

Abstract

The Pekeris coordinates provide a permutationally invariant set of coordinates for H$_3^+$. They are defined as linear combinations of the three internuclear distances that automatically fulfil the triangle inequality for all non-negative coordinate values. In this work, we test three discrete variable representations (DVR) for tightly converging the rovibrational energies up to and beyond the barrier to linearity using the Pekeris coordinates. The best performing representation is a cot-DVR-type approach adapted to the Pekeris problem. The two- and three-proton near coalescence region, which is also part of the direct product Pekeris grid but dynamically not relevant, is avoided by coordinate mapping and regulator functions.